Compositions and processes for depositing carbon-doped silicon-containing films

ABSTRACT

Described herein are compositions for depositing a carbon-doped silicon containing film comprising: a precursor comprising at least one compound selected from the group consisting of: an organoaminosilane having a formula of R 8 N(SiR 9 LH) 2 , wherein R 8 , R 9 , and L are defined herein. Also described herein are methods for depositing a carbon-doped silicon-containing film using the composition wherein the method is one selected from the following: cyclic chemical vapor deposition (CCVD), atomic layer deposition (ALD), plasma enhanced ALD (PEALD) and plasma enhanced CCVD (PECCVD).

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. Application Ser. No.16/398,209, filed Apr. 29, 2019, which is a continuation application ofU.S. Application Ser. No. 15/233,018, filed Aug. 10, 2016, which in turnclaims priority to U.S. Application Ser. No. 14/122,825, filed Jun. 4,2014, which in turn claims priority to U.S. Provisional Application No.61/493,031, filed on Jun. 3, 2011, the disclosures of which are herebyincorporated by reference.

BACKGROUND OF THE INVENTION

Precursor(s), particularly organoaminosilane precursors, that can beused for the deposition of silicon containing films, including but notlimited to, silicon oxide films, silicon nitride films, or siliconoxynitride films which further comprise carbon (referred to collectivelyherein as carbon-doped silicon-containing films) are described herein.In yet another aspect, described herein is the use of theorganoaminosilane precursor(s) for depositing silicon-containing in thefabrication of devices, such as, but not limited to, integrated circuitdevices. In these or other aspects, the organoaminosilane precursor(s)may be used for a variety of deposition processes, including but notlimited to, atomic layer deposition (“ALD”), chemical vapor deposition(“CVD”), plasma enhanced chemical vapor deposition (“PECVD”), lowpressure chemical vapor deposition (“LPCVD”), and atmospheric pressurechemical vapor deposition.

Several classes of compounds can be used as precursors for carbon-dopedsilicon-containing films. Examples of these compounds suitable for useas precursors include silanes, chlorosilanes, polysilazanes,aminosilanes, and azidosilanes. Inert carrier gas or diluents such as,but not limited, helium, hydrogen, nitrogen, etc., are also used todeliver the precursors to the reaction chamber.

Some important characteristics of a carbon-doped silicon-containing filmare wet etch resistance and hydrophobicity. Generally speaking, theintroduction of carbon to a silicon-containing film helps decrease thewet etch rate and increases the hydrophobicity. Additional advantages ofadding carbon to a silicon containing film is to lower the dielectricconstant or provide improvements to other electrical or physicalattributes of the film.

Further examples of precursors and processes for depositing carbon-dopedsilicon-containing films are provided in the following references.Applicants' patents, U.S. Pat. Nos. 7,875,556; 7,875,312; and 7,932,413,described classes of aminosilanes which are used for the deposition ofdielectric films, such as, for example, silicon oxide and siliconcarbonitride films in a chemical vapor deposition or atomic layerdeposition process.

Japanese Publ. No. JP 2010/275602 describes a material for chemicalvapor deposition for depositing a silicon-containing thin film that isrepresented by the formula HSiMe(R¹)(NR²R³) (R¹=NR⁴R⁵, C1-5 alkyl; R²,R⁴=H, C1-5 alkyl; R³, R⁵=C1-5 alkyl). The silicon-containing thin filmis formed by temperatures ranging from 300-500° C.

US Publ. No. 2008/0124946A1 describes a process for depositing a carboncontaining silicon oxide film, or a carbon containing silicon nitridefilm having enhanced etch resistance. The process comprises using astructure precursors containing silicon, a dopant precursor containingcarbon, and mixing the dopant precursors with the structure precursor toobtain a mixture having a mixing ratio of Rm (% weight of the dopantprecursor added to the structure precursor) between 2% and 85%; and aflow rate of Fm; providing a chemical modifier having a flow rate of Fc;having a flow ratio R2 defined as R2=Fm/Fc between 25% and 75%; andproducing the carbon containing silicon containing film or the carboncontaining silicon oxide film having enhanced etch resistance whereinthe etch resistance is increased with increasing incorporation of thecarbon.

US Publ. No. 2006/0228903 describes a process for fabricating a carbondoped silicon nitride layer using a first precursor which provides asource of silicon and a second precursor which adds carbon to the film.Examples of first precursor described in the '903 publication includehalogenated silanes and disilanes, aminosilanes, cyclodisilazanes,linear and branched silizanes, azidosilanes, substituted versions of1,2,4,5-tetraaza-3,6-disilacyclohexane, and silyl hydrazines. Examplesof the second precursor described in the '903 publication are alkylsilanes that have the general formula SiR₄ where R is any ligandincluding but not limited to hydrogen, alkyl and aryl (all R groups areindependent), alkyl polysilanes, halogenated alkyl silanes, carbonbridged silane precursors; and silyl ethanes/ethylene precursors.

US Publ. No. 2005/0287747A1 describes a process for forming a siliconnitride, silicon oxide, silicon oxynitride or silicon carbide film thatincludes adding at least one non-silicon precursor (such as a germaniumprecursor, a carbon precursor, etc.) to improve the deposition rateand/or makes possible tuning of properties of the film, such as tuningof the stress of the film.

U.S. Pat. No. 5744196A discloses the process comprises (a) heating asubstrate upon which SiO2 is to be deposited to approximately 150-500Deg in a vacuum maintained at approximately 50-750 m torr; (b)introducing into the vacuum an organosilane-containing feed and anO-containing feed, the organosilane contg.-feed consisting essentiallyof >=1 compds. having the general formula R¹Si(H₂)C_(x)(R⁴)₂Si(H₂)R²,where R¹, R²=C1-6 alkyl, alkenyl, alkynyl, or aryl, or R¹ and R² arecombined to form an alkyl chain Cx(R³)₂; R³=H, C_(x)H_(2x+1); x=1-6;R⁴=H, C_(y)H_(2y+1); and y=1-6; and (c) maintaining the temperature andvacuum, thereby causing a thin film of SiO₂ to deposit on the substrate.

Precursors and processes that are used in depositing carbon-dopedsilicon oxide films generally deposit the films at temperatures greaterthan 550° C. The trend of miniaturization of semiconductor devices andlow thermal budget requires lower process temperatures and higherdeposition rates. Further, there is a need in the art to provide novelprecursors or combinations of precursors that may allow for moreeffective control of the carbon content contained in the carbon-dopedsilicon containing film. Accordingly, there is a continuing need in theart to provide compositions of precursors for the deposition ofcarbon-doped silicon-containing films which provide films that exhibitone or more of the following attributes: lower relative etch rates,greater hydrophobicity, higher deposition rates, higher density,compared to films deposited using the individual precursors alone.

BRIEF SUMMARY OF THE INVENTION

Described herein are precursor compositions and methods using same forforming films comprising carbon-doped silicon (referred to herein assilicon containing films), such as, but not limited to, carbon-dopedstoichiometric or non-stoichiometric silicon oxide, carbon-dopedstoichiometric or non-stoichiometric silicon nitride, siliconoxynitride, silicon oxycarbide, silicon carbonitride, and combinationsthereof onto at least a portion of a substrate. In certain embodiments,the carbon-doped silicon-containing can have a carbon content of 2×10¹⁹carbon atom/cc or less of carbon as measured by measured by dynamicSecondary Ions Mass Spectrometry (SIMS). In alternative embodiments, thecarbon-doped silicon-containing films can have a carbon content thatranges from about 2×10¹⁹ carbon atom/cc to 2×10²² carbon atom/cc asmeasured by dynamic SIMS.

Also described herein are the methods to form carbon-doped siliconcontaining films or coatings on an object to be processed, such as, forexample, a semiconductor wafer. In one embodiment of the methoddescribed herein, a layer comprising silicon, carbon and oxygen isdeposited onto a substrate using the precursor composition describedherein and an oxidizing agent in a deposition chamber under conditionsfor generating a carbon-doped silicon oxide layer on the substrate. Inanother embodiment of the method described herein, a layer comprisingsilicon, carbon, and nitrogen is deposited onto a substrate using theprecursor composition described herein and an nitrogen containingprecursor in a deposition chamber under conditions for generating acarbon-doped silicon nitride layer on the substrate. In certainembodiments, the deposition method for depositing the carbon-dopedsilicon-containing film using the precursor composition described hereinis selected from the group consisting of cyclic chemical vapordeposition (CCVD), atomic layer deposition (ALD), plasma enhanced ALD(PEALD) and plasma enhanced CCVD (PECCVD).

In one aspect, there is provided a composition for depositing acarbon-doped silicon containing film comprising:

-   -   (a) a first precursor comprising at least one selected from the        group consisting of:        -   (i) an organoaminoalkylsilane having a formula of            R⁵Si(NR³R⁴)_(x)H_(3−x) wherein x=1, 2, 3;        -   (ii) an organoalkoxyalkylsilane having a formula of            R⁶Si(OR⁷)_(x)H_(3−x) wherein x=1, 2, 3;        -   (iii) an organoaminosilane having a formula of            R⁸N(SiR⁹(NR¹⁰R¹¹)H)₂;        -   (iv) an organoaminosilane having a formula of R⁸N(SiR⁹LH)₂;            and combinations thereof;            wherein R³, R⁴, and R⁷ are each independently selected from            the group consisting of a C₁ to C₁₀ linear or branched alkyl            group, a C₃ to C₁₀ cyclic alkyl group, a linear or branched            C₂ to C₁₀ alkenyl group, a linear or branched C₂ to C₁₀            alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀            saturated or unsaturated heterocyclic group; R⁵ and R⁶ are            each independently selected from the group consisting of a            C₁ to C₁₀ linear or branched alkyl group, a C₃ to C₁₀ cyclic            alkyl group, a linear or branched C₂ to C₁₀ alkenyl group, a            linear or branched C₂ to C₁₀ alkynyl group, a C₅ to C₁₀            aromatic group, and a C₃ to C₁₀ saturated or unsaturated            heterocyclic group, and a halide atom; R⁸ and R⁹ are each            independently selected from the group consisting of            hydrogen, C₁ to C₁₀ linear or branched alkyl, a C₃ to C₁₀            cyclic alkyl group, a linear or branched C₂ to C₁₀ alkenyl            group, a linear or branched C₂ to C₁₀ alkynyl group, a C₅ to            C₁₀ aromatic group, and a C₃ to C₁₀ saturated or unsaturated            heterocyclic group; and R¹⁰ and R¹¹ are each independently            selected from the group consisting of a C₁ to C₁₀ linear or            branched alkyl group, a C₃ to C₁₀ cyclic alkyl group, a            linear or branched C₂ to C₁₀ alkenyl group, a linear or            branched C₂ to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic            group, and a C₃ to C₁₀ saturated or unsaturated heterocyclic            group, and L=Cl, Br, or I; wherein R³ and R⁴ can form a            cyclic ring or an alkyl-substituted cyclic ring; and wherein            R¹⁰ and R¹¹ can form a cyclic ring or an alkyl-substituted            cyclic ring; and    -   (b) optionally a second precursor comprising an        organoaminosilane having a formula Si(NR¹R²)H₃ wherein R¹ and R²        are each independently selected from the group consisting of a        C₁ to C₁₀ linear or branched alkyl group, a C₃ to C₁₀ cyclic        alkyl group, a linear or branched C₂ to C₁₀ alkenyl group, a        linear or branched C₃ to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic        group, and a C₃ to C₁₀ saturated or unsaturated heterocyclic        group and wherein R¹ and R² can form a cyclic ring or an        alkyl-substituted cyclic ring.

In a further aspect, there is provided a composition for depositing acarbon-doped silicon containing film comprising:

-   -   a first precursor comprising at least one selected from the        group consisting of:        -   an organoaminoalkylsilane having a formula of            R⁵Si(NR³R⁴)_(x)H_(3−x), wherein x=1, 2, 3;        -   an organoalkoxyalkylsilane having a formula of            R⁶Si(OR⁷)_(x)H_(3−x), wherein x=1, 2, 3;        -   an organoaminosilane having a formula of            R⁸N(SiR⁹(NR¹⁰R¹¹)H)₂;        -   an organoaminosilane having a formula of R⁸N(SiR⁹LH)₂; and            combinations thereof;            wherein R³, R⁴, and R⁷ are each independently selected from            the group consisting of a C₁ to C₁₀ linear or branched alkyl            group, a C₃ to C₁₀ cyclic alkyl group, a linear or branched            C₂ to C₁₀ alkenyl group, a linear or branched C₂ to C₁₀            alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀            saturated or unsaturated heterocyclic group; R⁵ and R⁶ are            each independently selected from the group consisting of a            C₁ to C₁₀ linear or branched alkyl group, a C₃ to C₁₀ cyclic            alkyl group, a linear or branched C₂ to C₁₀ alkenyl group, a            linear or branched C₂ to C₁₀ alkynyl group, a C₅ to C₁₀            aromatic group, and a C₃ to C₁₀ saturated or unsaturated            heterocyclic group, and a halide atom; R⁸ and R⁹ are each            independently selected from the group consisting of            hydrogen, C₁ to C₁₀ linear or branched alkyl, a C₃ to C₁₀            cyclic alkyl group, a linear or branched C₂ to C₁₀ alkenyl            group, a linear or branched C₂ to C₁₀ alkynyl group, a C₅ to            C₁₀ aromatic group, and a C₃ to C₁₀ saturated or unsaturated            heterocyclic group; and R¹⁰ and R¹¹ are each independently            selected from the group consisting of a C₁ to C₁₀ linear or            branched alkyl group, a C₃ to C₁₀ cyclic alkyl group, a            linear or branched C₂ to C₁₀ alkenyl group, a linear or            branched C₂ to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic            group, and a C₃ to C₁₀ saturated or unsaturated heterocyclic            group, and L=Cl, Br, or I; wherein R³ and R⁴ can form a            cyclic ring or an alkyl-substituted cyclic ring; and wherein            R¹⁰ and R¹¹ can form a cyclic ring or an alkyl-substituted            cyclic ring; and    -   optionally a second precursor comprising an organoaminosilane        having a formula of R¹²Si(NR¹³R¹⁴)_(x)H_(3−x), wherein x=0, 1,        2, 3, and 4, wherein R¹², R¹³, and R¹⁴ are each independently        selected from the group consisting of H, a C₁ to C₁₀ linear or        branched alkyl group, a C₃ to C₁₀ cyclic alkyl group, a linear        or branched C₂ to C₁₀ alkenyl group, a linear or branched C₂ to        C₁₀ alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀        saturated or unsaturated heterocyclic group and wherein R¹³ and        R¹⁴ can form a cyclic ring or an alkyl-substituted cyclic ring.

In another aspect, there is provided a composition for depositing acarbon-doped silicon containing film comprising: a first precursorcomprising an organoaminoalkylsilane having a formula ofR⁵Si(NR³R⁴)_(x)H_(3−x), wherein x=1, 2, 3 wherein R³ and R⁴ are eachindependently selected from the group consisting of a C₁ to C₁₀ linearor branched alkyl group, a C₃ to C₁₀ cyclic alkyl group, a linear orbranched C₂ to C₁₀ alkenyl group, a linear or branched C₂ to C₁₀ alkynylgroup, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀ saturated orunsaturated heterocyclic group; R⁵ is selected from the group consistingof a C₁ to C₁₀ linear or branched alkyl group, a C₃ to C₁₀ cyclic alkylgroup, a linear or branched C₂ to C₁₀ alkenyl group, a linear orbranched C₂ to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃to C₁₀ saturated or unsaturated heterocyclic group, and a halide atom,and wherein R³ and R⁴ can form a cyclic ring or an alkyl-substitutedcyclic ring. In this or other embodiments, the composition furthercomprises a second precursor comprising an organoaminosilane having aformula Si(NR¹R²)H₃ wherein R¹ and R² are each independently selectedfrom the group consisting of a C₁ to C₁₀ linear or branched alkyl group,a C₃ to C₁₀ cyclic alkyl group, a linear or branched C₂ to C₁₀ alkenylgroup, a linear or branched C₃ to C₁₀ alkynyl group, a C₅ to C₁₀aromatic group, and a C₃ to C₁₀ saturated or unsaturated heterocyclicgroup and wherein R¹ and R² can form a cyclic ring or analkyl-substituted cyclic ring.

In a further aspect, there is provided a composition for depositing acarbon-doped silicon containing film comprising: a first precursorcomprising: an organoalkoxyalkylsilane having a formula ofR⁶Si(OR⁷)_(x)H_(3−x), wherein x=1, 2, 3 and wherein R⁷ is independentlyselected from the group consisting of a C₁ to C₁₀ linear or branchedalkyl group, a C₃ to C₁₀ cyclic alkyl group, a linear or branched C₂ toC₁₀ alkenyl group, a linear or branched C₂ to C₁₀ alkynyl group, a C₅ toC₁₀ aromatic group, and a C₃ to C₁₀ saturated or unsaturatedheterocyclic group; and R⁶ is independently selected from the groupconsisting of a C₁ to C₁₀ linear or branched alkyl group, a C₃ to C₁₀cyclic alkyl group, a linear or branched C₂ to C₁₀ alkenyl group, alinear or branched C₂ to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic group,and a C₃ to C₁₀ saturated or unsaturated heterocyclic group, and ahalide atom; R⁸ and R⁹ are each independently selected from the groupconsisting of hydrogen, C₁ to C₁₀ linear or branched alkyl, a C₃ to C₁₀cyclic alkyl group, a linear or branched C₂ to C₁₀ alkenyl group, alinear or branched C₂ to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic group,and a C₃ to C₁₀ saturated or unsaturated heterocyclic group. In this orother embodiments, the composition further comprises a second precursorcomprising an organoaminosilane having a formula Si(NR¹R²)H₃ wherein R¹and R² are each independently selected from the group consisting of a C₁to C₁₀ linear or branched alkyl group, a C₃ to C₁₀ cyclic alkyl group, alinear or branched C₂ to C₁₀ alkenyl group, a linear or branched C₂ toC₁₀ alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀ saturatedor unsaturated heterocyclic group and wherein R¹ and R² can form acyclic ring or an alkyl-substituted cyclic ring.

In yet another aspect, there is provided a composition for depositing acarbon-doped silicon containing film comprising: a first precursorcomprising: an organoaminosilane having a formula ofR⁸N(SiR⁹(NR¹⁰R¹¹)H)₂ wherein R⁸ and R⁹ are each independently selectedfrom the group consisting of hydrogen, C₁ to C₁₀ linear or branchedalkyl, a C₃ to C₁₀ cyclic alkyl group, a linear or branched C₂ to C₁₀alkenyl group, a linear or branched C₂ to C₁₀ alkynyl group, a C₅ to C₁₀aromatic group, and a C₃ to C₁₀ saturated or unsaturated heterocyclicgroup; and R¹⁰ and R¹¹ are each independently selected from the groupconsisting of a C₁ to C₁₀ linear or branched alkyl group, a C₃ to C₁₀cyclic alkyl group, a linear or branched C₂ to C₁₀ alkenyl group, alinear or branched C₂ to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic group,and a C₃ to C₁₀ saturated or unsaturated heterocyclic group; and whereinR¹⁰ and R¹¹ can form a cyclic ring or an alkyl-substituted cyclic ring.In this or other embodiments, the composition further comprises a secondprecursor comprising an organoaminosilane having a formula Si(NR¹R²)H₃wherein R¹ and R² are each independently selected from the groupconsisting of a C₁ to C₁₀ linear or branched alkyl group, a C₃ to C₁₀cyclic alkyl group, a linear or branched C₂ to C₁₀ alkenyl group, alinear or branched C₂ to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic group,and a C₃ to C₁₀ saturated or unsaturated heterocyclic group and whereinR¹ and R² can form a cyclic ring or an alkyl-substituted cyclic ring.

In another aspect, there is provided a method of forming a carbon-dopedsilicon oxide film via an atomic layer deposition process, the methodcomprising the steps of:

-   -   a. providing a substrate in a reactor;    -   b. introducing into the reactor a first precursor comprising at        least one compound selected from the group consisting of:        -   (i) an organoaminoalkylsilane having a formula of            R⁵Si(NR³R⁴)_(x)H_(3−x) wherein x=1, 2, 3;        -   (ii) an organoalkoxyalkylsilane having a formula of            R⁶Si(OR⁷)_(x)H_(3−x) wherein x=1, 2, 3;        -   (iii) an organoaminosilane having a formula of            R⁸N(SiR⁹(NR¹⁰R¹¹)H)₂;        -   (iv) an organoaminosilane having a formula of R⁸N(SiR⁹LH)₂            and combinations thereof;            wherein R³, R⁴, and R⁷ are each independently selected from            the group consisting of a C₁ to C₁₀ linear or branched alkyl            group, a C₃ to C₁₀ cyclic alkyl group, a linear or branched            C₂ to C₁₀ alkenyl group, a linear or branched C₂ to C₁₀            alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀            saturated or unsaturated heterocyclic group; R⁵ and R⁶ are            each independently selected from the group consisting of a            C₁ to C₁₀ linear or branched alkyl group, a C₃ to C₁₀ cyclic            alkyl group, a linear or branched C₂ to C₁₀ alkenyl group, a            linear or branched C₃ to C₁₀ alkynyl group, a C₅ to C₁₀            aromatic group, and a C₃ to C₁₀ saturated or unsaturated            heterocyclic group and a halide atom; R⁸ and R⁹ are each            independently selected from the group consisting of            hydrogen, C₁ to C₁₀ linear or branched alkyl, a C₃ to C₁₀            cyclic alkyl group, a linear or branched C₂ to C₁₀ alkenyl            group, a linear or branched C₂ to C₁₀ alkynyl group, a C₅ to            C₁₀ aromatic group, and a C₃ to C₁₀ saturated or unsaturated            heterocyclic group; and R¹⁰ and R¹¹ are each independently            selected from the group consisting of a C₁ to C₁₀ linear or            branched alkyl group, a C₃ to C₁₀ cyclic alkyl group, a            linear or branched C₂ to C₁₀ alkenyl group, a linear or            branched C₂ to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic            group, and a C₃ to C₁₀ saturated or unsaturated heterocyclic            group; L=Cl, Br, or I and wherein R³ and R⁴ can form a            cyclic ring or an alkyl-substituted cyclic ring; and wherein            R¹⁰ and R¹¹ can form a cyclic ring or an alkyl-substituted            cyclic ring;    -   c. purging the reactor with a purge gas;    -   d. introducing an oxygen source into the reactor;    -   e. introducing into the reactor a second precursor having the        following formula Si(NR¹R²)H₃ wherein R¹ and R² are each        independently selected from the group consisting of a C₁ to C₁₀        linear or branched alkyl group, a C₃ to C₁₀ cyclic alkyl group,        a linear or branched C₂ to C₁₀ alkenyl group, a linear or        branched C₂ to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic group,        and a C₃ to C₁₀ saturated or unsaturated heterocyclic group and        wherein R¹ and R² can form a cyclic ring or an alkyl-substituted        cyclic ring;    -   f. purging the reactor with a purge gas;    -   g. introducing an oxygen source into the reactor;    -   h. purging the reactor with a purge gas; and    -   i. repeating the steps b through h until a desired thickness of        the film is obtained. In one particular embodiment of the method        described herein, the precursor in step (b) comprises an        organoaminoalkylsilane described herein as (i). More        particularly, the precursor in step (b) comprises the        organaoaminoalkylsilane 2,6-dimethylpiperidinomethylsilane.

In another aspect, there is provided a method of forming a carbon-dopedsilicon nitride film via an atomic layer deposition process, the methodcomprising the steps of:

-   -   a. providing a substrate in a reactor;    -   b. introducing into the reactor a first precursor comprising at        least one compound selected from the group consisting of:        -   (i) an organoaminoalkylsilane having a formula of            R⁵Si(NR³R⁴)_(x)H_(3−x) wherein x=1, 2, 3;        -   (ii) an organoalkoxyalkylsilane having a formula of            R⁶Si(OR⁷)_(x)H_(3−x) wherein x=1, 2, 3;        -   (iii) an organoaminosilane having a formula of            R₈N(SiR⁹(NR¹⁰R₁₁)H)₂;        -   (iv) an organoaminosilane having a formula of R⁸N(SiR⁹LH)₂            and combinations thereof;            wherein R³, R⁴, and R⁷ are each independently selected from            the group consisting of a C₁ to C₁₀ linear or branched alkyl            group, a C₃ to C₁₀ cyclic alkyl group, a linear or branched            C₂ to C₁₀ alkenyl group, a linear or branched C₂ to C₁₀            alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀            saturated or unsaturated heterocyclic group; R⁵ and R⁶ are            each independently selected from the group consisting of a            C₁ to C₁₀ linear or branched alkyl group, a C₃ to C₁₀ cyclic            alkyl group, a linear or branched C₂ to C₁₀ alkenyl group, a            linear or branched C₃ to C₁₀ alkynyl group, a C₅ to C₁₀            aromatic group, and a C₃ to C₁₀ saturated or unsaturated            heterocyclic group and a halide atom; R⁸ and R⁹ are each            independently selected from the group consisting of            hydrogen, C₁ to C₁₀ linear or branched alkyl, a C₃ to C₁₀            cyclic alkyl group, a linear or branched C₂ to C₁₀ alkenyl            group, a linear or branched C₂ to C₁₀ alkynyl group, a C₅ to            C₁₀ aromatic group, and a C₃ to C₁₀ saturated or unsaturated            heterocyclic group; and R¹⁰ and R¹¹ are each independently            selected from the group consisting of a C₁ to C₁₀ linear or            branched alkyl group, a C₃ to C₁₀ cyclic alkyl group, a            linear or branched C₂ to C₁₀ alkenyl group, a linear or            branched C₂ to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic            group, and a C₃ to C₁₀ saturated or unsaturated heterocyclic            group; L=Cl, Br, or I and wherein R³ and R⁴ can form a            cyclic ring or an alkyl-substituted cyclic ring; and wherein            R¹⁰ and R¹¹ can form a cyclic ring or an alkyl-substituted            cyclic ring;    -   c. purging the reactor with a purge gas;    -   d. introducing a nitrogen source into the reactor;    -   e. introducing into the reactor a second precursor having the        following formula Si(NR¹R²)H₃ wherein R¹ and R² are each        independently selected from the group consisting of a C₁ to C₁₀        linear or branched alkyl group, a C₃ to C₁₀ cyclic alkyl group,        a linear or branched C₂ to C₁₀ alkenyl group, a linear or        branched C₂ to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic group,        and a C₃ to C₁₀ saturated or unsaturated heterocyclic group and        wherein R¹ and R² can form a cyclic ring or an alkyl-substituted        cyclic ring    -   f. purging the reactor with a purge gas;    -   g. introducing a nitrogen source into the reactor;    -   h. purging the reactor with a purge gas; and    -   i. repeating the steps b through h until a desired thickness of        the film is obtained. In one particular embodiment of the method        described herein, the precursor in step (b) comprises an        organoaminoalkylsilane described herein as (i). More        particularly, the precursor in step (b) comprises the        organaoaminoalkylsilane 2,6-dimethylpiperidinomethylsilane.

In another aspect, there is provided a method of forming a carbon-dopedsilicon oxide film via an atomic layer deposition process, the methodcomprising the steps of:

-   -   a. providing a substrate in a reactor;    -   b. introducing into the reactor a first precursor comprising at        least one compound selected from the group consisting of:        -   (v) an organoaminoalkylsilane having a formula of            R⁵Si(NR³R⁴)_(x)H_(3−x) wherein x=1, 2, 3;        -   (vi) an organoalkoxyalkylsilane having a formula of            R⁶Si(OR⁷)_(x)H_(3−x) wherein x=1, 2, 3;        -   (vii) an organoaminosilane having a formula of            R8N(SiR⁹(NR¹⁰R¹¹)H)₂;        -   (viii) an organoaminosilane having a formula of R⁸N(SiR⁹LH)₂            and combinations thereof;

wherein R³, R⁴, and R⁷ are each independently selected from the groupconsisting of a C₁ to C₁₀ linear or branched alkyl group, a C₃ to C₁₀cyclic alkyl group, a linear or branched C₂ to C₁₀ alkenyl group, alinear or branched C₂ to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic group,and a C₃ to C₁₀ saturated or unsaturated heterocyclic group; R⁵ and R⁶are each independently selected from the group consisting of a C₁ to C₁₀linear or branched alkyl group, a C₃ to C₁₀ cyclic alkyl group, a linearor branched C₂ to C₁₀ alkenyl group, a linear or branched C₃ to C₁₀alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀ saturated orunsaturated heterocyclic group and a halide atom; R⁸ and R⁹ are eachindependently selected from the group consisting of hydrogen, C₁ to C₁₀linear or branched alkyl, a C₃ to C₁₀ cyclic alkyl group, a linear orbranched C₂ to C₁₀ alkenyl group, a linear or branched C₂ to C₁₀ alkynylgroup, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀ saturated orunsaturated heterocyclic group; and R¹⁰ and R¹¹ are each independentlyselected from the group consisting of a C₁ to C₁₀ linear or branchedalkyl group, a C₃ to C₁₀ cyclic alkyl group, a linear or branched C₂ toC₁₀ alkenyl group, a linear or branched C₂ to C₁₀ alkynyl group, a C₅ toC₁₀ aromatic group, and a C₃ to C₁₀ saturated or unsaturatedheterocyclic group; L=Cl, Br, or I and wherein R³ and R⁴ can form acyclic ring or an alkyl-substituted cyclic ring; and wherein R¹⁰ and R¹¹can form a cyclic ring or an alkyl-substituted cyclic ring;

-   -   c. purging the reactor with a purge gas;    -   d. introducing an oxygen source into the reactor;    -   e. introducing into the reactor a second precursor having a        formula of R¹²Si(NR¹³R¹⁴)_(x)H_(3−x), wherein x=0, 1, 2, 3, and        4, wherein R¹², R¹³, and R¹⁴ are each independently selected        from the group consisting of H, a C₁ to C₁₀ linear or branched        alkyl group, a C₃ to C₁₀ cyclic alkyl group, a linear or        branched C₂ to C₁₀ alkenyl group, a linear or branched C₂ to C₁₀        alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀        saturated or unsaturated heterocyclic group and wherein R¹³ and        R¹⁴ can form a cyclic ring or an alkyl-substituted cyclic ring;    -   f. purging the reactor with a purge gas;    -   g. introducing an oxygen source into the reactor;    -   h. purging the reactor with a purge gas; and    -   i. repeating the steps b through h until a desired thickness of        the film is obtained. In one particular embodiment of the method        described herein, the precursor in step (b) comprises an        organoaminoalkylsilane described herein as (i). More        particularly, the precursor in step (b) comprises the        organaoaminoalkylsilane 2,6-dimethylpiperidinomethylsilane.

In another aspect, there is provided a method of forming a carbon-dopedsilicon nitride film via an atomic layer deposition process, the methodcomprising the steps of:

-   -   a. providing a substrate in a reactor;    -   b. introducing into the reactor a first precursor comprising at        least one compound selected from the group consisting of:        -   (v) an organoaminoalkylsilane having a formula of            R⁵Si(NR³R⁴)_(x)H_(3−x). wherein x=1, 2, 3;        -   (vi) an organoalkoxyalkylsilane having a formula of            R⁶Si(OR⁷)_(x)H_(3−x) wherein x=1, 2, 3;        -   (vii) an organoaminosilane having a formula of            R8N(SiR⁹(NR¹⁰R¹¹)H)₂;        -   (viii) an organoaminosilane having a formula of R⁸N(SiR⁹LH)₂            and combinations thereof;            wherein R³, R⁴, and R⁷ are each independently selected from            the group consisting of a C₁ to C₁₀ linear or branched alkyl            group, a C₃ to C₁₀ cyclic alkyl group, a linear or branched            C₂ to C₁₀ alkenyl group, a linear or branched C₂ to C₁₀            alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀            saturated or unsaturated heterocyclic group; R⁵ and R⁶ are            each independently selected from the group consisting of a            C₁ to C₁₀ linear or branched alkyl group, a C₃ to C₁₀ cyclic            alkyl group, a linear or branched C₂ to C₁₀ alkenyl group, a            linear or branched C₃ to C₁₀ alkynyl group, a C₅ to C₁₀            aromatic group, and a C₃ to C₁₀ saturated or unsaturated            heterocyclic group and a halide atom; R⁸ and R⁹ are each            independently selected from the group consisting of            hydrogen, C₁ to C₁₀ linear or branched alkyl, a C₃ to C₁₀            cyclic alkyl group, a linear or branched C₂ to C₁₀ alkenyl            group, a linear or branched C₂ to C₁₀ alkynyl group, a C₅ to            C₁₀ aromatic group, and a C₃ to C₁₀ saturated or unsaturated            heterocyclic group; and R¹⁰ and R¹¹ are each independently            selected from the group consisting of a C₁ to C₁₀ linear or            branched alkyl group, a C₃ to C₁₀ cyclic alkyl group, a            linear or branched C₂ to C₁₀ alkenyl group, a linear or            branched C₂ to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic            group, and a C₃ to C₁₀ saturated or unsaturated heterocyclic            group; L=Cl, Br, or I and wherein R³ and R⁴ can form a            cyclic ring or an alkyl-substituted cyclic ring; and wherein            R¹⁰ and R¹¹ can form a cyclic ring or an alkyl-substituted            cyclic ring;    -   c. purging the reactor with a purge gas;    -   d. introducing a nitrogen source into the reactor;    -   e. introducing into the reactor a second precursor having a        formula of R¹²Si(NR¹³R¹⁴)_(x)H_(3−x) wherein x=0, 1, 2, 3, and        4, wherein R¹², R¹³, and R¹⁴ are each independently selected        from the group consisting of H, a C₁ to C₁₀ linear or branched        alkyl group, a C₃ to C₁₀ cyclic alkyl group, a linear or        branched C₂ to C₁₀ alkenyl group, a linear or branched C₂ to C₁₀        alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀        saturated or unsaturated heterocyclic group and wherein R¹³ and        R¹⁴ can form a cyclic ring or an alkyl-substituted cyclic ring;    -   f. purging the reactor with a purge gas;    -   g. introducing a nitrogen source into the reactor;    -   h. purging the reactor with a purge gas; and    -   i. repeating the steps b through h until a desired thickness of        the film is obtained. In one particular embodiment of the method        described herein, the precursor in step (b) comprises an        organoaminoalkylsilane described herein as (i). More        particularly, the precursor in step (b) comprises the        organaoaminoalkylsilane 2,6-dimethylpiperidinomethylsilane.

BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 provides the mass spectroscopy (MS) spectrum of2,6-dimethylpiperidinomethylsilane described in Example 1.

FIG. 2 provides the thermal gravimetric analysis (TGA) and differentialscanning calorimetry (DCS) analysis of2,6-dimethylpiperidinomethylsilane.

FIG. 3 provides an IR spectra comparison of films deposited using2,6-dimethylpiperidinosilane and 2,6-dimethylpiperidinomethylsilane at atemperature of 100° C.

FIG. 4 provides an IR spectra comparison of films deposited using2,6-dimethylpiperidinomethylsilane at different temperatures (e.g., 100°C., 150° C., and 300° C.).

DETAILED DESCRIPTION OF THE INVENTION

Described herein are compositions comprising one or more precursors andprocesses for depositing a carbon-doped silicon-containing film viaatomic layer deposition (ALD), cyclic chemical vapor deposition (CCVD)or plasma enhanced ALD (PEALD) or plasma enhanced CCVD (PECCVD) usingthe precursor compositions. The compositions described herein arecomprised of, consist essentially of, or consist of, a first precursorcomprising at least one compound selected from the group of compoundshaving the following formulas: (i) R⁵Si(NR³R⁴)_(x)H_(3−x); (ii)R⁶Si(OR⁷)_(x)H_(3-x); (iii) an organoaminosilane having a formula ofR⁸N(SiR⁹(NR¹⁰R¹¹)H)₂; and combinations of (i), (ii), and (iii) whereinR³, R⁴, and R⁷ are each independently selected from the group consistingof a C₁ to C₁₀ linear or branched alkyl group, a C₃ to C₁₀ cyclic alkylgroup, a linear or branched C₂ to C₁₀ alkenyl group, a linear orbranched C₃ to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃to C₁₀ saturated or unsaturated heterocyclic group; R⁵ and R⁶ are eachindependently selected from the group consisting of a C₁ to C₁₀ linearor branched alkyl group, a C₃ to C₁₀ cyclic alkyl group, a linear orbranched C₂ to C₁₀ alkenyl group, a linear or branched C₃ to C₁₀ alkynylgroup, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀ saturated orunsaturated heterocyclic group and a halide atom; R⁸ and R⁹ are eachindependently selected from the group consisting of hydrogen, C₁ to C₁₀linear or branched alkyl, a C₃ to C₁₀ cyclic alkyl group, a linear orbranched C₂ to C₁₀ alkenyl group, a linear or branched C₃ to C₁₀ alkynylgroup, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀ saturated orunsaturated heterocyclic group; and R¹⁰ and R¹¹ are each independentlyselected from the group consisting of a C₁ to C₁₀ linear or branchedalkyl group, a C₃ to C₁₀ cyclic alkyl group, a linear or branched C₂ toC₁₀ alkenyl group, a linear or branched C₃ to C₁₀ alkynyl group, a C₅ toC₁₀ aromatic group, and a C₃ to C₁₀ saturated or unsaturatedheterocyclic group; and x=1, 2, or 3, and wherein R³ and R⁴ can form acyclic ring or an alkyl-substituted cyclic ring; and wherein R¹⁰ and R¹¹can form a cyclic ring or an alkyl-substituted cyclic ring. In certainembodiments, the composition further comprises a second precursorcomprising an organoaminosilane having a formula Si(NR¹R²)H₃ wherein R¹and R² are each independently selected from the group consisting of a C₁to C₁₀ linear or branched alkyl group, a C₃ to C₁₀ cyclic alkyl group, alinear or branched C₂ to C₁₀ alkenyl group, a linear or branched C₃ toC₁₀ alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀ saturatedor unsaturated heterocyclic group and wherein R¹ and R² can form acyclic ring or an alkyl-substituted cyclic ring.

The precursors in the composition described herein are typically highpurity volatile liquid precursor chemical that are vaporized anddelivered to a deposition chamber or reactor as a gas to deposit asilicon containing film via CVD or ALD processes for semiconductor orother devices. The selection of precursor materials for depositiondepends upon the desired resultant dielectric material or film. Forexample, a precursor material may be chosen for its content of chemicalelements, its stoichiometric ratios of the chemical elements, and/or theresultant silicon containing film or coating that are formed under CVD.The precursor material used in the compositions may also be chosen forvarious other characteristics such as cost, relatively low toxicity,handling characteristics, ability to maintain liquid phase at roomtemperature, volatility, molecular weight, and/or other considerations.In certain embodiments, the precursors in the composition describedherein can be delivered to the reactor system by any number of means,preferably using a pressurizable stainless steel vessel fitted with theproper valves and fittings, to allow the delivery of liquid phaseprecursor to the deposition chamber or reactor.

The precursors in the compositions described herein exhibits a balanceof reactivity and stability that makes them ideally suitable as CVD orALD precursors. With regard to reactivity, certain precursors may haveboiling points that are too high to be vaporized and delivered to thereactor to be deposited as a film on a substrate. Precursors havinghigher relative boiling points require that the delivery container andlines need to be heated at or above the boiling point of the precursorto prevent condensation or particles from forming in the container,lines, or both. With regard to stability, other organosilane precursorsmay form silane (SiH₄) as they degrade. Silane is pyrophoric at roomtemperature or it can spontaneously combust which presents safety andhandling issues. Moreover, the formation of silane and other by-productsdecreases the purity level of the precursor and changes as small as 1 to2% in chemical purity may be considered unacceptable for reliablesemiconductor manufacture. In certain embodiments, the precursors in thecompositions described herein comprise less than 2% by weight, or lessthan 1% by weight, or less than 0.5% by weight of by-product (such asthe corresponding bis-silane byproduct) after being stored for a 6months or greater, or one year or greater time period which isindicative of being shelf stable. In addition to the foregoingadvantages, in certain embodiments, such as for depositing a siliconoxide or silicon nitride film using an ALD or PEALD deposition method,the organoaminosilane precursor described herein may be able to deposithigh density materials at relatively low deposition temperatures, e.g.,500° C. or less, or 400° C. or less, 300° C. or less, 200° C. or less,100° C. or less, or 50° C. or less. In certain embodiments, thecomposition described herein can deposit the carbon-doped siliconcontaining film at a deposition temperature of about 250° C. or less,200° C. or less, 100° C. or less, or 50° C. or less.

The compositions described herein are used to deposit carbon-dopedsilicon-containing film that exhibit a higher wet etch resistance and alower hydrophobicity compared to silicon-containing films that do notcontain carbon. Not being bound by theory, the introduction of carbon toa silicon-containing film, particularly in lower alkyl forms (e.g., Me,Et, Pr, groups), helps decrease the wet etch rate and increases thehydrophobicity. Selective etching is particularly important insemiconductor patterning process. Additional advantages of adding carbonto a silicon containing film is to lower the dielectric constant orother electrical or physical attributes of the film. It is believed thatthe strength of the Si—C bond formed from the lower alkyl substituentson silicon, particularly the silicon-methyl bond, is sufficient for itto remain at least partially intact during film formation according tothe processes described in this invention. The residual organic carbonin the silicon-containing film imparts reduced dielectric constant andenhances hydrophobicity and also reduces the etch rate using diluteaqueous hydrofluoric acid.

As previously discussed, the compositions described herein contain atleast one precursors comprising an organic group, a nitrogen atom and asilicon atom. The first precursor is comprised of at least one compoundselected from the compounds having the following formulas: (i)R⁵Si(NR³R⁴)_(x)H_(3−x), (ii) R⁶Si(OR⁷)_(x)H_(3−x), (iii)R⁸N(SiR⁹(NR¹⁰R¹¹)H)₂ and combinations thereof. In certain embodiments,the precursors described herein alone or in combination, are deliveredvia a liquid injection apparatus. The carbon content in the resultingfilms can be adjusted by one or more of the following: the amount ofcarbon contained in the precursor, the type of carbon contained in theprecursor, deposition conditions, in certain embodiments, the number ofcycles of the first precursor relative to the number of cycles of thesecond precursor in a cyclic CVD or ALD process, in certain embodiments,the ratio of first precursor to second precursor in the composition, orcombinations thereof.

In one embodiment, the composition for depositing a carbon-doped siliconcontaining film comprises a first precursor(s) comprising anorganoaminoalkylsilane having a formula of R⁵Si(NR³R⁴)_(x)H_(3−x)wherein x=1, 2, 3 and wherein R³, R⁴, and R⁷ are each independentlyselected from the group consisting of a C₁ to C₁₀ linear or branchedalkyl group, a C₃ to C₁₀ cyclic alkyl group, a linear or branched C₂ toC₁₀ alkenyl group, a linear or branched C₂ to C₁₀ alkynyl group, a C₅ toC₁₀ aromatic group, and a C₃ to C₁₀ saturated or unsaturatedheterocyclic group; R⁵ is selected from the group consisting of a C₁ toC₁₀ linear or branched alkyl group, a C₃ to C₁₀ cyclic alkyl group, alinear or branched C₂ to C₁₀ alkenyl group, a linear or branched C₃ toC₁₀ alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀ saturatedor unsaturated heterocyclic group and a halide atom; and wherein R³ andR⁴ can form a cyclic ring or an alkyl-substituted cyclic. In certainembodiments of the organoaminoalkylsilane having a formula ofR⁵Si(NR³R⁴)_(x)H_(3−x), R³ and R⁴ can be combined to form a cyclicgroup. In these embodiments, the cyclic group may be a carbocyclic orheterocyclic group. The cyclic group can be saturated or, alternatively,unsaturated. In other embodiments of the oragnoaminoalkylsilane having aformula of R⁵Si(NR³R⁴)_(x)H_(3−x), R³ and R⁴ are not combined to form acyclic group.

In another embodiment, the composition for depositing a carbon-dopedsilicon containing film comprises a first precursor(s) comprising anorganoalkoxyalkylsilane having a formula of R⁶Si(OR⁷)_(x)H_(3−x),wherein x=1, 2, 3 and wherein R⁷ is selected from the group consistingof a C₁ to C₁₀ linear or branched alkyl group, a C₃ to C₁₀ cyclic alkylgroup, a linear or branched C₂ to C₁₀ alkenyl group, a linear orbranched C₃ to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃to C₁₀ saturated or unsaturated heterocyclic group; and R⁶ is selectedfrom the group consisting of a C₁ to C₁₀ linear or branched alkyl group,a C₃ to C₁₀ cyclic alkyl group, a linear or branched C₂ to C₁₀ alkenylgroup, a linear or branched C₃ to C₁₀ alkynyl group, a C₅ to C₁₀aromatic group, and a C₃ to C₁₀ saturated or unsaturated heterocyclicgroup, and a halide atom.

In a further embodiment, the composition for depositing a carbon-dopedsilicon containing film comprises a first precursor(s) comprising anorganoaminosilane having a formula of R⁸N(SiR⁹(NR¹⁰R¹¹)H)₂ wherein R⁸and R⁹ are each independently selected from the group consisting ofhydrogen, C₁ to C₁₀ linear or branched alkyl group, a C₃ to C₁₀ cyclicalkyl group, a linear or branched C₂ to C₁₀ alkenyl group, a linear orbranched C₃ to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃to C₁₀ saturated or unsaturated heterocyclic group; R¹⁰ and R¹¹ are eachindependently selected from the group consisting of a C₁ to C₁₀ linearor branched alkyl group, a C₃ to C₁₀ cyclic alkyl group, a linear orbranched C₂ to C₁₀ alkenyl group, a linear or branched C₃ to C₁₀ alkynylgroup, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀ saturated orunsaturated heterocyclic group; and wherein R¹⁰ and R¹¹ can form acyclic ring or an alkyl-substituted cyclic ring. In certain embodimentsof the organoaminosilane having a formula of R⁸N(SiR⁹(NR¹⁰R¹¹)H)₂, R¹⁰and R¹¹ can be combined to form a cyclic group. In these embodiments,the cyclic group may be a carbocyclic or heterocyclic group. The cyclicgroup can be saturated or, alternatively, unsaturated. In otherembodiments of the organoaminosilane having a formula ofR⁸N(SiR⁹(NR¹⁰R¹¹)H)₂, R¹⁰ and R¹¹ are not combined to form a cyclicgroup.

In another embodiment, the first precursor comprises anorganoaminosilane with a formula of R⁸N(SiR⁹LH)₂ wherein R⁸ and R⁹ areindependently selected from the group consisting of hydrogen, C₁ to C₁₀linear or branched alkyl, a C₃ to C₁₀ cyclic alkyl group, a linear orbranched C₂ to C₁₀ alkenyl group, a linear or branched C₃ to C₁₀ alkynylgroup, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀ saturated orunsaturated heterocyclic group; and L is a halide selected from thegroup consisting of Cl, Br, I.

In certain embodiments, the composition for depositing a carbon-dopedsilicon containing film further comprises a second precursor comprisingan organoaminosilane having a formula Si(NR¹R²)H₃ wherein R¹ and R² areeach independently selected from the group consisting of a C₁ to C₁₀linear or branched alkyl group, a C₃ to C₁₀ cyclic alkyl group, a linearor branched C₂ to C₁₀ alkenyl group, a linear or branched C₃ to C₁₀alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀ saturated orunsaturated heterocyclic group and wherein R¹ and R² can form a cyclicring or an alkyl-substituted cyclic ring. In certain embodiments of theorganoaminosilane having formula Si(NR¹R²)H₃, R¹ and R² can be linkedtogether to form a ring. In these or other embodiments, the ringcomprises a heterocyclic ring. The ring, or alternatively, heterocyclicring, may be saturated or unsaturated. In alternative embodiments of theorganoaminosilane having formula Si(NR¹R²)H₃, R¹ and R² are not linkedtogether to form a ring.

In an alternative embodiment, the optional second precursor can comprisean organoaminoalkylsilane having a formula of R¹²Si(NR¹³R¹⁴)_(x)H_(3−x),wherein x=0, 1, 2, 3, and 4, wherein R¹², R¹³, and R¹⁴ are eachindependently selected from the group consisting of H, a C₁ to C₁₀linear or branched alkyl group, a C₃ to C₁₀ cyclic alkyl group, a linearor branched C₂ to C₁₀ alkenyl group, a linear or branched C₂ to C₁₀alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀ saturated orunsaturated heterocyclic group. In certain embodiments of havingformula, R¹³ and R¹⁴ can be linked together to form a ring. In these orother embodiments, the ring comprises a heterocyclic ring. The ring, oralternatively, heterocyclic ring, may be saturated or unsaturated. Inalternative embodiments of the organoaminosilane having formula, R¹³ andR¹⁴ are not linked together to form a ring.

In the foregoing formulas for the first and second precursors andthroughout the description, the term “alkyl” denotes a linear orbranched functional group having from 1 to 10, or 3 to 10, or 1 to 6carbon atoms. Exemplary linear alkyl groups include, but are not limitedto, methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Exemplarybranched alkyl groups include, but are not limited to, isopropyl,isobutyl, sec-butyl, tert-butyl, iso-pentyl, tert-pentyl, isohexyl, andneohexyl. In certain embodiments, the alkyl group may have one or morefunctional groups such as, but not limited to, an alkyl group, an alkoxygroup, a dialkylamino group or combinations thereof, attached thereto.In other embodiments, the alkyl group does not have one or morefunctional groups attached thereto. The alkyl group may be saturated or,alternatively, unsaturated.

In the foregoing formulas and throughout the description, the term“cyclic alkyl” denotes a cyclic group having from 3 to 10 or 5 to 10atoms. Exemplary cyclic alkyl groups include, but are not limited to,cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. In certainembodiments, the cyclic alkyl group may have one or more C₁ to C₁₀linear, branched substituents, or substituents containing oxygen ornitrogen atoms. In this or other embodiments, the cyclic alkyl group mayhave one or more linear or branched alkyls or alkoxy groups assubstituents, such as, for example, a methylcyclohexyl group or amethoxycyclohexyl group

In the foregoing formulas and throughout the description, the term“aryl” denotes an aromatic cyclic functional group having from 5 to 10carbon atoms or from 6 to 10 carbon atoms. Exemplary aryl groupsinclude, but are not limited to, phenyl, benzyl, chlorobenzyl, tolyl,and o-xylyl.

In the foregoing formulas and throughout the description, the term“alkenyl group” denotes a group which has one or more carbon-carbondouble bonds and has from 2 to 20 or from 2 to 10 or from 2 to 6 carbonatoms.

In the foregoing formulas and throughout the description, the term“alkynyl group” denotes a group which has one or more carbon-carbontriple bonds and has from 2 to 20 or from 2 to 10 or from 2 to 6 carbonatoms.

In the foregoing formulas and through the description, the term“unsaturated” as used herein means that the functional group,substituent, ring or bridge has one or more carbon double or triplebonds. An example of an unsaturated ring can be, without limitation, anaromatic ring such as a phenyl ring. The term “saturated” means that thefunctional group, substituent, ring or bridge does not have one or moredouble or triple bonds.

In certain embodiments, the term “carbocyclic or heterocyclic ring”denotes a carbocyclic or heterocyclic ring. Exemplary cyclic or alkylsubstituted cyclic ring groups include, but not limited to, cyclohexyl,cyclopentyl, pyrrolidino, piperidino, morpholino,2,5-dimethylpyrrolidino, 2,6-dimethylpiperidino, or otheralkyl-substituted derivatives.

In certain embodiments, one or more of the alkyl group, alkenyl group,alkynyl group, aryl group, and/or aromatic group in the foregoingformulas may be substituted or have one or more atoms or group of atomssubstituted in place of, for example, a hydrogen atom. Exemplarysubstituents include, but are not limited to, oxygen, sulfur, halideatoms (e.g., F, Cl, I, or Br), nitrogen, and phosphorous. In otherembodiments, one or more of the alkyl group, alkenyl group, alkynylgroup, alkoxyalkyl group, alkoxy group, alkylaminoalkyl group, aromaticand/or aryl group in the foregoing formulas may be unsubstituted.

Some specific examples of methyl-substituted compounds which can be usedas the first precursor in the compositions described herein include,without limitation, bis(diemethylamino)methylsilane,diethylaminomethylsilane, t-butylaminomethylsilane, andisopropylaminomethylsilane.

In certain embodiments, the first precursor, second precursor, or bothhaving the foregoing formulas has one or more substituents comprisingoxygen atoms. In these embodiments, the need for an oxygen source duringthe deposition process may be avoided. In other embodiments, the firstprecursor, second precursor, or both having the foregoing formulas haveone or more substituents comprising oxygen atoms also uses an oxygensource.

In certain embodiments, the composition described herein comprises afirst precursor or organoaminoalkylsilane having the formulaR⁵Si(NR³R⁴)_(x)H_(3−x), wherein x=1, 2, 3 and R³, R⁴, and R⁵ are thesubstituents described herein. The organoaminoalkylsilane having theformula R⁵Si(NR³R⁴)_(x)H_(3−x) can be prepared by reacting an alkylamine, R³R⁴NH, with a halosilane or an aminosilane in an organic solventor solvent mixture with removal of hydrogen halide, or amine. Thehydrogen halide may be conveniently removed by precipitation upon addinga tertiary amine and forming the corresponding amine hydrochloride salt.In one embodiment, an organoaminoalkylsilane having the formulaR⁵Si(NR³R⁴)_(x)H_(3−x) wherein x=1 and R⁵=Cl can be prepared, forexample, in the reaction represented by Equation (1) below and R³, R⁴are the substituents described herein:

In certain embodiments, the composition described herein comprises afirst precursor or organoaminoalkylsilane having the formulaR⁵Si(NR³R⁴)_(x)H_(3−x) wherein x=1, 2, 3 and R³, R⁴, and R⁵ are thesubstituents described herein. The organoaminoalkylsilane having theformula R⁵Si(NR³R⁴)_(x)H_(3−x) can be prepared by reacting an alkylamine, R³R⁴NH, with a halosilane or an aminosilane in an organic solventor solvent mixture with removal of hydrogen halide or amine. Thehydrogen halide may be conveniently removed by precipitation upon addinga tertiary amine and forming the corresponding amine hydrochloride salt.In one embodiment, an organoaminoalkylsilane having the formulaR⁵Si(NR³R⁴)_(x)H_(3−x) wherein x=1 and R⁵=Cl can be prepared, forexample, in the reaction represented by Equation (1) below and R³, R⁴are the substituents described herein:

Another organoaminoalkylsilane having the formula,R⁵Si(NR³R⁴)_(x)H_(3−x) wherein x=1 and R⁵ is a C₁ to C₁₀ linear orbranched alkyl can be prepared, for example, in the reaction representedby Equation (2) below and R³, R⁴, and R⁵ are the substituents describedherein:

In another embodiment, the composition described herein comprises afirst precursor having the formula R⁸N(SiR⁹(NR¹⁰R¹¹)H)₂ wherein R⁸, R⁹,R¹⁰ and R¹¹ are substituent described herein. In one particularembodiment of the foregoing formula, R⁹ is hydrogen, and the compoundcan be prepared, for example, in a method described in the followingEquation 3 and 4 below and wherein R⁸, R⁹, R¹⁰ and R¹¹ are substituentdescribed herein:

In yet another embodiment, the first precursor comprises anorganoaminosilane having a formula of R⁸N(SiR⁹LH)₂ wherein R⁸ and R⁹ arethe substituents described herein and L=Cl, Br, I. In one particularembodiment of the foregoing formula wherein L=Cl, the organoaminosilanescan be prepared, for example, in a method described in followingEquation 5 below and wherein R⁸ and R⁹ are substituent described herein:

In embodiments wherein the composition comprises a first and secondprecursor, the first precursor the second precursor have similar boilingpoints (b.p.) or the difference between the b.p. of the first precursorand the b.p. of the second precursor is 40° C. or less, 30° C. or less,or 20° C. or less, or 10° C. Alternatively, the difference between theboiling of the first and second precursors ranges from any one or moreof the following end-points: 0, 10, 20, 30, or 40° C. Examples ofsuitable ranges of b.p. difference include without limitation, 0 to 40°C., 20° to 30° C., or 10° to 30° C. In these embodiments, the first andthe second precursors can be delivered via direct liquid injection,vapor draw or bubbling while still keeping the same liquid ratio in thegas phase.

In embodiments wherein the composition comprises a first and secondprecursor, the amount of first precursor in the composition, by weightpercentage of the overall composition, ranges from 0.5% by weight to99.5% or from 10% by weight to 75% with the balance being the secondprecursor or any additional precursors added thereto. In these or otherembodiments, the amount of second precursor in the composition by weightpercentage ranges from 0.5% by weight to 99.5% or from 10% by weight to75% with the balance being the first precursor(s) or any additionalprecursors. In an alternative embodiment, the composition comprises 100%of the first precursor.

One embodiment of the present invention is related to a precursorformulation consisting of an organoaminosilane with a formula of Si(NR¹R²)H_(3−x) and an organoaminoalkylsilane with a formula ofR⁵Si(NR³R⁴)_(x)H_(3−x) wherein R¹⁻⁴ are selected from the groupconsisting of C₁ to C₁₀ linear or branched alkyl, alkyl containing otherelements such as oxygen or nitrogen, cyclic alkyl, alkenyl, alkynyl,aromatic hydrocarbon; R⁵ is selected from the group consisting of C₁ toC₁₀ linear or branched alkyl, alkyl containing oxygen or nitrogen,cyclic alkyl, alkenyl, alkynyl, aromatic hydrocarbon, Cl, Br, and I; R¹and R² can form a cyclic or alkyl substituted cyclic ring; R³ and R⁴ canalso form a cyclic or alkyl substituted cyclic ring; x=1, 2, 3.Preferably, R¹⁻² and R³⁻⁴ are independently selected from the same C₁ toC₁₀ linear or branched alkyls.

Table I provides exemplary compositions comprising both first and secondprecursors wherein the first precursor comprises anorganoaminoalkylsilane of the formula R⁵Si(NR³R⁴)_(x)H_(3−x) whereinx=1, 2, 3 and wherein Me (methyl), Et (ethyl), ^(n)Pr (normal propyl),^(i)Pr (iso-propyl), ^(n)Bu (normal butyl), ^(i)Bu (iso-butyl), ^(s)Bu(secondary butyl), and ^(t)Bu (tertiary butyl) and the optional secondprecursor comprises an organoaminosilane having the following generalformula Si(NR¹R²)H₃. In these or other embodiments, the exemplarycompositions may be provided in a stainless steel vessel, such aswithout limitation, a pressurizable vessel for storage and delivery tothe reactor. In this or other embodiments, the vessel is fitted with theproper valves and fittings to allow the delivery of the first and secondprecursor to the reactor for a CVD or an ALD process. In certainembodiments, such vessels can also have means for mixing the first andoptional second precursors, if present, or can be premixed.Alternatively, the first and optional second precursors can bemaintained in separate vessels or in a single vessel having separationmeans for maintaining the precursors in the composition separate duringstorage.

TABLE I Exemplary Precursor Compositions Optional Second No. FirstPrecursor Precursor 1. (^(i)Pr₂N)R⁵SiH₂ wherein R⁵ is selected(^(i)Pr₂N)SiH₃ from the group consisting of Me (methyl), Et (ethyl),^(n)Pr (normal propyl), ^(i)Pr (iso-propyl), ^(n)Bu (normal butyl),^(i)Bu (iso-butyl), ^(s)Bu (secondary butyl), ^(t)Bu (tertiary butyl),isomers of pentyl, vinyl, phenyl, and alkyl substituted phenyl 2.(^(s)Bu₂N)R⁵SiH₂ wherein R⁵ is selected (^(s)Bu₂N)SiH₃ from the groupconsisting of Me, Et, ^(n)Pr, ^(i)Pr, ^(n)Bu, ^(i)Bu, ^(s)Bu, ^(t)Bu,isomers of pentyl, vinyl, phenyl, and alkyl substituted phenyl 3.(2,6-dimethylpiperidino)R⁵SiH₂ (2,6-dimethyl- wherein R⁵ is selectedfrom the group piperidino)SiH₃ consisting of Me, Et, ^(n)Pr, _(i)Pr,^(n)Bu, ^(i)Bu, ^(s)Bu, ^(t)Bu, isomers of pentyl, vinyl, phenyl, andalkyl substituted phenyl 4. (phenylmethylamino)R⁵SiH₂ wherein(phenylmethylamino) R⁵ is selected from the group SiH₃ consisting of Me,Et, ^(n)Pr, ^(i)Pr, ^(n)Bu, ^(i)Bu, ^(s)Bu, ^(t)Bu, isomers of pentyl,vinyl, phenyl, and alkyl substituted phenyl

The method used to form the silicon-containing silicon containing filmsor coatings are deposition processes. Examples of suitable depositionprocesses for the method disclosed herein include, but are not limitedto, cyclic CVD (CCVD), MOCVD (Metal Organic CVD), thermal chemical vapordeposition, plasma enhanced chemical vapor deposition (“PECVD”), highdensity PECVD, photon assisted CVD, plasma-photon assisted (“PPECVD”),cryogenic chemical vapor deposition, chemical assisted vapor deposition,hot-filament chemical vapor deposition, CVD of a liquid polymerprecursor, deposition from supercritical fluids, and low energy CVD(LECVD). In certain embodiments, the metal containing films aredeposited via atomic layer deposition (ALD), plasma enhanced ALD (PEALD)or plasma enhanced cyclic CVD (PECCVD) process. As used herein, the term“chemical vapor deposition processes” refers to any process wherein asubstrate is exposed to one or more volatile precursors, which reactand/or decompose on the substrate surface to produce the desireddeposition. As used herein, the term “atomic layer deposition process”refers to a self-limiting (e.g., the amount of film material depositedin each reaction cycle is constant), sequential surface chemistry thatdeposit films of materials onto substrates of varying compositions.Although the precursors, reagents and sources used herein may besometimes described as “gaseous”, it is understood that the precursorscan be either liquid or solid which are transported with or without aninert gas into the reactor via direct vaporization, bubbling orsublimation. In some case, the vaporized precursors can pass through aplasma generator. In one embodiment, the silicon containing film isdeposited using an ALD process. In another embodiment, the siliconcontaining film is deposited using a CCVD process. In a furtherembodiment, the silicon containing film is deposited using a thermal CVDprocess. The term “reactor” as used herein, includes without limitation,reaction chamber or deposition chamber.

In certain embodiments, the method disclosed herein avoids pre-reactionof the precursors by using ALD or CCVD methods that separate theprecursor(s) prior to and/or during the introduction to the reactor. Inthis connection, deposition techniques such as ALD or CCVD processes areused to deposit the carbon-doped silicon containing film. In oneembodiment, the film is deposited via an ALD process by exposing thesubstrate surface alternatively to the one or more the first precursor,oxygen source if an oxide film, nitrogen-containing source if a nitridefilm, second precursor, or other precursor or reagent. Film growthproceeds by self-limiting control of surface reaction, the pulse lengthof each precursor or reagent, and the deposition temperature. However,once the surface of the substrate is saturated, the film growth ceases.

As previously mentioned, in certain embodiments, such as for depositinga carbon-doped silicon containing film such as a silicon oxide or asilicon nitride film using an ALD, CCVD (PECCVD), or PEALD depositionmethod, the compositions described herein may be able to deposit filmsat relatively low deposition temperatures, e.g., of 500° C. or less, or400° C. or less, 300° C. or less, 200° C. or less, 100° C. or less, or50° C. or less or room temperature. In these or other embodiments, thesubstrate (deposition) temperature ranges from any one or more of thefollowing end-points: 0, 25, 50, 100, 200, 300, 400, or 500° C. Examplesof these ranges are, without limitation, 0 to 100° C., 25 to 50° C.,100° to 300° C., or 100° C. to 500° C. In one particular embodiment, thedeposition temperature is below 200° C. which allows carbon to beincorporated into the resulting films, providing films such as carbondoped silicon oxide with low etching rate.

Depending upon the deposition method, in certain embodiments, the one ormore silicon-containing precursors may be introduced into the reactor ata predetermined molar volume, or from about 0.1 to about 1000micromoles. In this or other embodiments, the silicon-containing and/ororganoaminosilane precursor may be introduced into the reactor for apredetermined time period. In certain embodiments, the time periodranges from about 0.001 to about 500 seconds.

In certain embodiments, the silicon containing films deposited using themethods described herein is formed in the presence of oxygen using anoxygen source, reagent or precursor comprising oxygen. An oxygen sourcemay be introduced into the reactor in the form of at least one oxygensource and/or may be present incidentally in the other precursors usedin the deposition process. Suitable oxygen source gases may include, forexample, water (H₂O) (e.g., deionized water, purifier water, and/ordistilled water), water plasma, oxygen (O₂), peroxide (O₃), oxygenplasma, ozone (O₃), NO, NO₂, carbon monoxide (CO), carbon dioxide (CO₂)and combinations thereof. In certain embodiments, the oxygen sourcecomprises an oxygen source gas that is introduced into the reactor at aflow rate ranging from about 1 to about 2000 square cubic centimeters(sccm) or from about 1 to about 1000 sccm. The oxygen source can beintroduced for a time that ranges from about 0.1 to about 100 seconds.In one particular embodiment, the oxygen source comprises water having atemperature of 10° C. or greater. In embodiments wherein the film isdeposited by an ALD or a cyclic CVD process, the precursor pulse canhave a pulse duration that is greater than 0.01 seconds, and the oxygensource can have a pulse duration that is less than 0.01 seconds, whilethe water pulse duration can have a pulse duration that is less than0.01 seconds. In yet another embodiment, the purge duration between thepulses that can be as low as 0 seconds or is continuously pulsed withouta purge in-between. The oxygen source or reagent is provided in amolecular amount less than a 1:1 ratio to the silicon precursor, so thatat least some carbon is retained in the as deposited silicon containingfilm.

In certain embodiments, the silicon containing films comprise siliconand nitrogen. In these embodiments, the silicon containing filmsdeposited using the methods described herein are formed in the presenceof nitrogen-containing source. A nitrogen-containing source may beintroduced into the reactor in the form of at least one nitrogen sourceand/or may be present incidentally in the other precursors used in thedeposition process. Suitable nitrogen-containing source gases mayinclude, for example, ammonia, hydrazine, monoalkylhydrazine,dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogenplasma, nitrogen/hydrogen plasma, and mixture thereof. In certainembodiments, the nitrogen-containing source comprises an ammonia plasmaor hydrogen/nitrogen plasma source gas that is introduced into thereactor at a flow rate ranging from about 1 to about 2000 square cubiccentimeters (sccm) or from about 1 to about 1000 sccm. Thenitrogen-containing source can be introduced for a time that ranges fromabout 0.1 to about 100 seconds. In embodiments wherein the film isdeposited by an ALD or a cyclic CVD process, the precursor pulse canhave a pulse duration that is greater than 0.01 seconds, and thenitrogen-containing source can have a pulse duration that is less than0.01 seconds, while the water pulse duration can have a pulse durationthat is less than 0.01 seconds. In yet another embodiment, the purgeduration between the pulses that can be as low as 0 seconds or iscontinuously pulsed without a purge in-between.

The deposition methods disclosed herein may involve one or more purgegases. The purge gas, which is used to purge away unconsumed reactantsand/or reaction byproducts, is an inert gas that does not react with theprecursors. Exemplary purge gases include, but are not limited to, argon(Ar), nitrogen (N₂), helium (He), neon, hydrogen (H₂), and mixturesthereof. In certain embodiments, a purge gas such as Ar is supplied intothe reactor at a flow rate ranging from about 10 to about 2000 sccm forabout 0.1 to 1000 seconds, thereby purging the unreacted material andany byproduct that may remain in the reactor.

The respective step of supplying the precursor(s), oxygen source, thenitrogen-containing source, and/or other precursors, source gases,and/or reagents may be performed by changing the time for supplying themto change the stoichiometric composition of the resulting siliconcontaining film.

Energy is applied to the at least one of the precursor,nitrogen-containing oxygen-containing source, reducing agent, otherprecursors or combination thereof to induce reaction and to form thesilicon containing film or coating on the substrate. Such energy can beprovided by, but not limited to, thermal, plasma, pulsed plasma, heliconplasma, high density plasma, inductively coupled plasma, X-ray, e-beam,photon, remote plasma methods, and combinations thereof. In certainembodiments, a secondary RF frequency source can be used to modify theplasma characteristics at the substrate surface. In embodiments whereinthe deposition involves plasma, the plasma-generated process maycomprise a direct plasma-generated process in which plasma is directlygenerated in the reactor, or alternatively a remote plasma-generatedprocess in which plasma is generated outside of the reactor and suppliedinto the reactor.

The organoaminosilane precursors and/or other silicon-containingprecursors may be delivered to the reaction chamber such as a CVD or ALDreactor in a variety of ways. In one embodiment, a liquid deliverysystem may be utilized. In an alternative embodiment, a combined liquiddelivery and flash vaporization process unit may be employed, such as,for example, the turbo vaporizer manufactured by MSP Corporation ofShoreview, Minn., to enable low volatility materials to bevolumetrically delivered, which leads to reproducible transport anddeposition without thermal decomposition of the precursor. In liquiddelivery formulations or compositions, the precursors described hereinmay be delivered in neat liquid form, or alternatively, may be employedin solvent formulations or compositions comprising same. Thus, incertain embodiments the precursor formulations may include solventcomponent(s) of suitable character as may be desirable and advantageousin a given end use application to form a film on a substrate.

In another embodiment, a vessel for depositing a silicon containing filmcomprising the composition comprising, consisting essentially of, orconsisting of, the first and optionally second precursors are describedherein. In one particular embodiment, the vessel comprises at least onepressurizable vessel (preferably of stainless steel) fitted with theproper valves and fittings to allow the delivery of the first and secondprecursor to the reactor for a CVD or an ALD process. In this or otherembodiments, the first and optionally second precursors are provided ina pressurizable vessel comprised of stainless steel and the purity ofthe precursor is 98% by weight or greater or 99.5% or greater which issuitable for the majority of semiconductor applications. In certainembodiments, such vessels can also have means for mixing the first andoptional second precursors, if present, or can be premixed.Alternatively, the first and optional second precursors can bemaintained in separate vessels or in a single vessel having separationmeans for maintaining the precursors in the composition separate duringstorage.

As previously mentioned, the purity level of the precursor(s) in thecomposition is sufficiently high enough to be acceptable for reliablesemiconductor manufacturing. In certain embodiments, the precursorsdescribed herein comprise less than 2% by weight, or less than 1% byweight, or less than 0.5% by weight of one or more of the followingimpurities: free amines, halides, and higher molecular weight species.Higher purity levels of the precursors described herein can be obtainedthrough one or more of the following processes: purification,adsorption, and/or distillation.

In certain embodiments, the gas lines connecting from the precursorcanisters to the reaction chamber are heated to one or more temperaturesdepending upon the process requirements and the container or containers(depending upon whether the first and optionally second precursors (incertain embodiments) are delivered separately or together) is kept atone or more temperatures for bubbling. In other embodiments, a solutioncomprising the first and optionally second precursor (depending uponwhether the first and, if present optionally second, precursors aredelivered separately or together) is injected into a vaporizer kept atone or more temperatures for direct liquid injection.

A flow of argon and/or other gas may be employed as a carrier gas tohelp deliver the vapor of the precursors to the reaction chamber duringthe precursor pulsing. In certain embodiments, the reaction chamberprocess pressure is about 1 Torr.

In a typical ALD or CCVD process, the substrate such as a silicon oxidesubstrate is heated on a heater stage in a reaction chamber that isexposed to the silicon-containing precursor initially to allow thecomplex to chemically adsorb onto the surface of the substrate.

A purge gas such as argon purges away unabsorbed excess complex from theprocess chamber. After sufficient purging, a nitrogen-containing sourcemay be introduced into reaction chamber to react with the absorbedsurface followed by another gas purge to remove reaction by-productsfrom the chamber. The process cycle can be repeated to achieve thedesired film thickness.

In this or other embodiments, it is understood that the steps of themethods described herein may be performed in a variety of orders, may beperformed sequentially or concurrently (e.g., during at least a portionof another step), and any combination thereof. The respective step ofsupplying the precursors and the nitrogen-containing source gases may beperformed by varying the duration of the time for supplying them tochange the stoichiometric composition of the resulting siliconcontaining film.

In certain embodiments, the method to deposit the carbon-dopedsilicon-containing film is an ALD or cyclic CVD method and thecomposition comprises a first and second precursor. In these or otherembodiments, the order of the first and second precursor can bedelivered in any one or more of the following manners wherein A refersto the delivery of the first precursor and B refers to the delivery ofthe second precursor: ABABABAB . . . wherein the first and secondprecursors are alternated until the desired number of cycles arecompleted; AAAAABBBBB . . . wherein the first precursor is introducedfor the first half of the process cycles and the second precursor isintroduced for the second half of the process cycles; and combinationsthereof. In these or other embodiments, the number of process cycles ofthe first precursor relative to the second precursor can be optimized toallow for a gradient of carbon within the carbon-containing siliconfilm.

The method disclosed herein forms the carbon doped silicon oxide filmsusing a precursor composition and an oxygen source. In one particularembodiment, the method comprises the following steps:

-   Step 1. Contacting vapors generated from a composition comprising an    first precursor comprising an organoalkoxyalkylsilane, and    optionally a second precursor comprising an organoaminosilane, with    a substrate to chemically sorb the precursors on the heated    substrate;-   Step 2. Purging away any unsorbed precursors;-   Step 3. Introducing an oxygen source on the heated substrate to    react with the sorbed precursors; and,-   Step 4. Purging away any unreacted oxygen source.-   The steps 1 through 4 are repeated until a desired thickness is    achieved.

In another embodiment, the method comprises the following steps:

-   Step 1. Contacting vapors generated from a first precursor with a    substrate to chemically sorb the precursor on the heated substrate,    the first precursor which is at least one compound selected from the    compounds having the following formulas:    R⁵Si(NR³R⁴)_(x)H_(3−x)  (a)    R⁶Si(OR⁷)_(x)H_(3−x)  (b)    R⁸N(SiR⁹(NR¹⁰R¹¹)H)₂  (c)    wherein R³, R⁴, and R⁷ are each independently selected from the    group consisting of a C₁ to C₁₀ linear or branched alkyl group, a C₃    to C₁₀ cyclic alkyl group, a linear or branched C₂ to C₁₀ alkenyl    group, a linear or branched C₂ to C₁₀ alkynyl group, a C₅ to C₁₀    aromatic group, and a C₃ to C₁₀ saturated or unsaturated    heterocyclic group; R⁵ and R⁶ are each independently selected from    the group consisting of a C₁ to C₁₀ linear or branched alkyl group,    a C₃ to C₁₀ cyclic alkyl group, a linear or branched C₂ to C₁₀    alkenyl group, a linear or branched C₂ to C₁₀ alkynyl group, a C₅ to    C₁₀ aromatic group, and a C₃ to C₁₀ saturated or unsaturated    heterocyclic group, and a halide atom; R⁸ and R⁹ are each    independently selected from the group consisting of hydrogen, C₁ to    C₁₀ linear or branched alkyl, a C₃ to C₁₀ cyclic alkyl group, a    linear or branched C₂ to C₁₀ alkenyl group, a linear or branched C₂    to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀    saturated or unsaturated heterocyclic group; and R¹⁰ and R¹¹ are    each independently selected from the group consisting of a C₁ to C₁₀    linear or branched alkyl group, a C₃ to C₁₀ cyclic alkyl group, a    linear or branched C₂ to C₁₀ alkenyl group, a linear or branched C₂    to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀    saturated or unsaturated heterocyclic group; wherein R³ and R⁴ can    form a cyclic ring or an alkyl-substituted cyclic ring; and wherein    R¹⁰ and R¹¹ can form a cyclic ring or an alkyl-substituted cyclic    ring; L=Cl, Br, I;-   Step 2. Purging away any unsorbed precursors;-   Step 3. Introducing an oxygen source on the heated substrate to    react with the sorbed silicon precursor;-   Step 4. Purging away any unreacted oxygen source;-   Step 5. Optionally contacting vapors generated from an optional    second precursor with a substrate to chemically sorb the second    precursor on the heated substrate, wherein the second precursor    compound has the formula Si(NR¹R²)H₃ wherein R¹ and R² are each    independently selected from the group consisting of a C₁ to C₁₀    linear or branched alkyl group, a C₃ to C₁₀ cyclic alkyl group, a    linear or branched C₂ to C₁₀ alkenyl group, a linear or branched C₂    to C₁₀ alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀    saturated or unsaturated heterocyclic group and wherein R¹ and R²    can form a cyclic ring or an alkyl-substituted cyclic ring;-   Step 6. Purging away any unsorbed precursors;-   Step 7. Introducing an oxygen source on the heated substrate to    react with the sorbed silicon precursor;-   Step 8. Purging away any unreacted oxygen source.-   The steps 1 through 8 are repeated until a desired thickness is    achieved.

In certain embodiments, the carbon-doped silicon containing filmsdescribed herein have a dielectric constant of 6 or less. In these orother embodiments, the films can a dielectric constant of about 5 orbelow, or about 4 or below, or about 3.5 or below. However, it isenvisioned that films having other dielectric constants (e.g., higher orlower) can be formed depending upon the desired end-use of the film. Anexample of the carbon-doped silicon containing film that is formed usingthe precursor compositions and processes described herein has theformulation Si_(x)O_(y)C_(z)N_(v)H_(w) wherein Si ranges from about 10%to about 40%; O ranges from about 0% to about 65%; C ranges from about0% to about 75% or from about 0% to about 50%; N ranges from about 0% toabout 75% or from about 0% to 50%; and H ranges from about 0% to about50% atomic percent weight % wherein x+y+z+v+w=100 atomic weight percent,as determined, for example, by XPS or other means.

As mentioned previously, the method described herein may be used todeposit a carbon-doped silicon-containing film on at least a portion ofa substrate. Examples of suitable substrates include but are not limitedto, silicon, SiO₂, Si₃N₄, OSG, FSG, silicon carbide, hydrogenatedsilicon carbide, silicon nitride, hydrogenated silicon nitride, siliconcarbonitride, hydrogenated silicon carbonitride, boronitride,antireflective coatings, photoresists, organic polymers, porous organicand inorganic materials, metals such as copper and aluminum, anddiffusion barrier layers such as but not limited to TiN, Ti(C)N, TaN,Ta(C)N, Ta, W, or WN and transparent amorphous oxide semiconductor(TAOS) or metal oxide materials include a-IGZO (amorphous gallium indiumzinc oxide), zinc oxide. The films are compatible with a variety ofsubsequent processing steps such as, for example, chemical mechanicalplanarization (CMP) and anisotropic etching processes.

The deposited films have applications, which include, but are notlimited to, computer chips, optical devices, magnetic informationstorages, coatings on a supporting material or substrate,microelectromechanical systems (MEMS), nanoelectromechanical systems,thin film transistor (TFT), and liquid crystal displays (LCD).

The following examples illustrate the method for preparingorganoaminosilane precursors as well as deposited silicon-containingfilms described herein and are not intended to limit it in any way.

EXAMPLES Example 1: Preparation of 2,6-dimethylpiperidino(methyl)silane

2,6-dimethylpiperidino(chloro)silane was prepared by dissolving 0.052Nm³ of dichlorosilane in 4.36 L of hexanes in a 6 L stirred reactor at−20° C. under a nitrogen atmosphere. To this solution was added 244 g oftriethylamine and then 260 g of cis-2,6-dimethylpiperidine was addedslowly with continuous agitation while maintaining the temperature at−20° C. Once the addition was complete, the mixture was allowed to warmto 20° C. and stirred for 16 h. A voluminous white precipitate formed,which was removed by filtration. The precipitate was rinsed with hexane.The filtrate combined with the rinses contained2,6-dimethylpiperidino(chloro)silane, which was isolated by stripping atreduced pressure to remove the hexanes. Further purification wasobtained by simple distillation of the residue at 100° C. under reducedpressure. The identity of 2,6-dimethylpiperidino(chloro)silane wasdetermined by mass spectrometry which showed peaks at 177 (M+), 162(M-CH₃) which are consistent with the molecular weight (177.75) of2,6-dimethylpiperidino(chloro)silane.

A 130 g of 2,6-dimethylpiperidino(chloro)silane prepared as describedabove was dissolved in 386 g of tetrahydrofuran and placed in a 2 Lreactor under an inert atmosphere. The solution was chilled to −20° C.and then 247 g of 3 molar methylmagnesium chloride solution intetrahydrofuran was added gradually with stirring over 60 minutes whilemaintaining the temperature at −20° C. The mixture was then allowed towarm to 20° C. over 30 minutes and then allowed to stir at thattemperature for 18 h. A heavy white precipitate was observed. Themixture was filtered and the precipitate was rinsed with an additional100 mL of tetrahydrofuran. The tetrahydrofuran from these combinedfiltrates was removed by simple distillation at reduced pressure. Theresulting yellow slurry was extracted with 400 mL of hexanes and thesolids were removed by filtration and rinsed with two portions of 50 mLof hexanes. The hexanes were stripped from this combined filtrate toproduce crude product that was further purified by simple distillationto provide 70.4 g of product. The identity of the material wasdetermined by mass spectrometry (see FIG. 2 ), which showed peaks at 157(M+), 142 (M-CH₃ and are consistent with the molecular weight (157.33)of 2,6-dimethylpiperidinomethylsilane. Gas chromatography with thermalconductivity detection indicates a purity of approximately 97% byweight. The boiling point was measured by DSC to be ˜173° C. atatmospheric pressure (see FIG. 2 ).

Three 10 cc stainless steel containers were carefully washed and bakedout at 175° C. prior to use. Each was loaded with an ampoule containinga 2 ml sample of 2,6-dimethylpiperidinomethylsilane. The ampoules werethen stored in constant temperature environments using laboratory ovenspre-set at 100° C.±2° C. for three days. The samples were evaluated bygas chromatography (GC) to determine the extent of degradation and theresults are shown in FIG. 2 . The average purity after heating showedvirtually no change, demonstrating it has excellent thermal stabilityand can be employed as a suitable precursor for reliable semi-conductorprocesses.

Example 2: Atomic Layer Deposition of Silicon-Containing Films

Atomic layers depositions of silicon-containing films were conductedusing the following precursors: 2,6-dimethylpiperidinosilane and2,6-dimethylpiperidinomethylsilane. The depositions were performed on alaboratory scale ALD processing tool. All gases (e.g., purge andreactant gas or precursor and oxygen source) were preheated to 100° C.prior to entering the deposition zone. Gases and precursor flow rateswere controlled with ALD diaphragm valves having high speed actuation.The substrates used in the deposition were 12 inch length silicon stripshaving thermocouples attached on a sample holder to confirm thesubstrate temperature. Depositions were performed using ozone as theoxygen source gas and the process parameters of the depositions areprovided in Table II.

TABLE II Process for Atomic Layer Deposition of Silicon-containing Filmswith Ozone Step 1 6 Nitrogen Purge of Flow 1.5 Purges out unreactedseconds Reactor slpm N₂ chemical from reactor (sec) Step 2 6 sec Chamberevacuation <100 mT Prepare the reactor for the precursor dose Step 3 2sec Close throttle valve Increases precursor resonance time Step 4 Vari-Dose Reactor pressure able Organoaminosilane typically <1T duringPrecursor dose Step 5 6 sec Nitrogen Purge of Flow 1.5 Purges outunreacted Reactor slpm N₂ chemical from reactor Step 6 6 sec Chamberevacuation <100 mT Prepare the reactor for the organoaminosilaneprecursor dose Step 7 2 sec Close throttle valve Increases theorganoaminosilane precursor resonance time Step 8 4 sec Dose Ozone O₃ at18-20% post generator, P =<8T

The resultant silicon-containing films were characterized for depositionrate and refractive index. Thickness and refractive indices of the filmswas measured using a FilmTek 2000SE ellipsometer by fitting thereflection data from the film to a pre-set physical model (e.g., theLorentz Oscillator model).

Wet etch rate was performed using 1% solution of 49% hydrofluoric (HF)acid in deionized water. Thermal oxide wafers were used as reference foreach test. Films thickness of both samples and comparative silicon oxidereference were measured with ellipsometer before and after etch. Siliconoxide films with carbon dopant have lower wet etch rate than siliconoxide films.

Film composition was analyzed with dynamic secondary ions massspectrometry (SIMS) technique. Fourier Transform Infrared (FTIR)spectrometry is used to confirm film structure. Absorbance in IR spectrais normalized with film thickness for comparison. Table III is summaryof the deposition temperature, deposition rate, refractive index, wetetch rate and carbon content measured by the Dynamic Secondary Ion MassSpectroscopy (SIMS). The silicon-containing films were deposited usingthe following methods described below.

Method (a) describes the formation of silicon-containing films using2,6-dimethylpiperidinosilane at three different substrate temperatures:300° C., 150° C. and 100° C. using the following process steps:

-   Step 1. Contacting vapors of 2,6-dimethylpiperidinosilane-   Step 2. Purging away any unsorbed 2,6-dimethylpiperidinosilane-   Step 3. Introducing ozone to react with the sorbed    2,6-dimethylpiperidinosilane-   Step 4. Purging away any unreacted ozone-   The above steps for Method (a) were repeated 500 times. The    deposited films do not show any significant C—H signatures at    2800-2960 cm⁻¹ or Si—CH₃ peak at ˜1250 cm⁻¹, as confirmed with FTIR.

Method (b) describes the formation of silicon-containing films using2,6-dimethylpiperidinomethylsilane at three different substratetemperatures: 300° C., 150° C. and 100° C. using the following processsteps:

-   Step 1. Contacting vapors of 2,6-dimethylpiperidinomethylsilane-   Step 2. Purging away any unsorbed 2,6-dimethylpiperidinomethylsilane-   Step 3. Introducing ozone to react with the sorbed    2,6-dimethylpiperidinomethylsilane-   Step 4. Purging away any unreacted ozone-   The steps were repeated for 500 cycles. Film deposited at 300° C.    showed a very similar IR signature as the    2,6-dimethylpiperidinosilane in Method (a) (e.g., no C—H signatures    at 2800-2960 cm⁻¹ and Si—CH₃ signature at ˜1250 cm⁻¹). Both C—H and    Si—CH₃ absorbance peaks occurred in films deposited at 150° C. and    stronger at 100° C.

Method (c) describes the formation of silicon-containing films usingalternating doses of the first precursor2,6-dimethylpiperidinomethylsilane and the second precursor2,6-dimethylpiperidinosilane at a substrate temperature of 100° C.;

-   Step 1. Contacting vapors of 2,6-dimethylpiperidinosilane-   Step 2. Purging away any unsorbed 2,6-dimethylpiperidinosilane-   Step 3. Introducing ozone to react with the sorbed    2,6-dimethylpiperidinosilane-   Step 4. Purging away any unreacted ozone-   Step 5. Contacting vapors of 2,6-dimethylpiperidinomethylsilane-   Step 6. Purging away any unsorbed    2,6-dimethylpiperidinomethylsilane;-   Step 7. Introducing ozone to react with the sorbed    2,6-dimethylpiperidinomethylsilane-   Step 8. Purging away any unreacted ozone-   The steps were repeated for 250 times.

TABLE III Summary of Resulting Silicon-containing Films using Methods(a) through (c) Wet Carbon Deposition Deposition etch Contenttemperature rate Refractive rate (# of Precursor (° C.) (Å/cycle) index(Å/min) atoms/cc) 2,6-dimethylpiperidinosilane 300 1.86 1.455 5.43 2 ×10¹⁹ (Method (a)) 2,6-dimethylpiperidinosilane 150 1.96 1.464 5.25 6 ×10¹⁹ (Method (a)) 2,6-dimethylpiperidinosilane 100 1.90 1.465 5.78 1 ×10²⁰ (Method (a)) 2,6- 300 1.24 1.473 5.13 2 × 10¹⁹dimethylpiperidinomethylsilane (Method (b)) 2,6- 150 0.58 1.513 3.07 3 ×10²¹ dimethylpiperidinomethylsilane (Method (b)) 2,6- 100 0.57 1.5171.18 2 × 10²² dimethylpiperidinomethylsilane (Method (b))2,6-dimethylpiperidinosilane 100 1.57 1.464 2.43 6 × 10²¹ and 2,6-dimethylpiperidinomethylsilane (Method (c))

Referring to Table III, the wet etch rates for silicon-containing filmsusing 2,6-dimethylpiperidinosilane showed no improvement regardless ofdeposition temperatures which is consistent with no carbon incorporationinto the films. However, unexpectedly, silicon-containing filmsdeposited at 300° C. using 2,6-dimethylpiperidinomethylsilane shows verysimilar IR signature as the films from 2,6-dimethylpiperidinosilane,i.e. no C—H signatures at 2800-2960 cm⁻¹ and Si—CH₃ signature at ˜1250cm⁻¹, although it was hoped that the Si—CH₃ group in2,6-dimethylpiperidinomethylsilane would be incorporated into theresulting silicon-containing films. Further, both C—H and Si—CH₃absorbance peaks occurred in films deposited at 150° C. and werestronger at 100° C. in films deposited withdimethylpiperidinomethylsilane. The wet etch rate is directly correlatedwith the amount of carbon incorporated into the films, i.e. the higherthe carbon content, the lower the wet etch rate. The carbon content inthe films deposited at 300° C. using either 2,6-dimethylpiperidinosilaneor 2,6-dimethylpiperidinomethylsilane deposited were very similar at2×10¹⁹ atoms/cc, indicating that the ozone effectively oxidized theSi—CH₃ group in 2,6-dimethylpiperidinomethylsilane. However, loweringthe deposition temperature from 300° C. to 150° C. or 100° C. increasedthe carbon incorporation into films due to less effective oxidation oforganoaminosilanes. Importantly, the effect is more pronounced for filmsdeposited from 2,6 dimethylpiperidinomethylsilane at temperature of 100°C., showing two orders of magnitude more carbon atoms. Additionally, notto be bound by theory, it is speculated that the amount of carbon in thefilms can also be adjusted by several other methods such as decreasingozone pulse time, decreasing ozone concentration, alternating layers ofcarbon doped silicon containing film as well as co-depositing carbondoped silicon containing layer with non-carbon doped silicon containingfilms.

FIG. 3 shows the IR spectra comparison between2,6-dimethylpiperidinosilane and 2,6-dimethylpiperidinomethylsilanedeposited at 100° C. FIG. 4 provides a comparison among2,6-dimethylpiperidinomethylsilane films deposited at differenttemperatures. This example demonstrates that the carbon content of thesilicon-containing can be tuned via varying deposition temperature orusing two different organoaminosilanes.

The invention claimed is:
 1. A method of forming a carbon-doped siliconnitride film via an atomic layer deposition process, the methodcomprising the steps of: a. providing a substrate in a reactor; b.introducing into the reactor a precursor comprising at least oneorganoaminosilane having a formula of R⁸N(SiR⁹LH)₂, wherein R⁸ isselected from the group consisting of a C₃ to C₁₀ linear or branchedalkyl group, a C₃ to C₁₀ cyclic alkyl group, a linear or branched C2 toC₁₀ alkenyl group, a linear or branched C2 to C₁₀ alkynyl group, a C₅ toC₁₀ aromatic group, and a C₃ to C₁₀ saturated or unsaturatedheterocyclic group; R⁹ selected from the group consisting of hydrogen,C₁ to C₁₀ linear or branched alkyl, a C₃ to C₁₀ cyclic alkyl group, alinear or branched C2 to C₁₀ alkenyl group, a linear or branched C₂ toC₁₀ alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀ saturatedor unsaturated heterocyclic group; and L is selected from the groupconsisting of Cl, Br, and I; c. purging the reactor with a purge gas; d.introducing a nitrogen source into the reactor wherein the nitrogensource is selected from the group consisting of ammonia, hydrazine,monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen,ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma, and mixturethereof; and e. purging the reactor with a purge gas, wherein steps bthrough e are repeated until a desired thickness of the film isobtained.
 2. A method of forming a carbon-doped silicon oxide film viaan atomic layer deposition process, the method comprising the steps of:a. providing a substrate in a reactor; b. introducing into the reactorat least one compound selected from the group consisting of: anorganoaminosilane having a formula of R⁸N(SiR⁹LH)₂, wherein R⁸ isselected from the group consisting of a C₃ to C₁₀ linear or branchedalkyl group, a C₃ to C₁₀ cyclic alkyl group, a linear or branched C2 toC₁₀ alkenyl group, a linear or branched C₂ to C₁₀ alkynyl group, a C₅ toC₁₀ aromatic group, and a C₃ to C₁₀ saturated or unsaturatedheterocyclic group; R⁹ selected from the group consisting of hydrogen,C₁ to C₁₀ linear or branched alkyl, a C₃ to C₁₀ cyclic alkyl group, alinear or branched C₂ to C₁₀ alkenyl group, a linear or branched C₂ toC₁₀ alkynyl group, a C₅ to C₁₀ aromatic group, and a C₃ to C₁₀ saturatedor unsaturated heterocyclic group; and L is selected from the groupconsisting of Cl, Br, and I; c. purging the reactor with a purge gas; d.introducing an oxygen source into the reactor wherein the oxygen sourceis selected from the group consisting of water, water plasma, oxygen,peroxide, oxygen plasma, ozone, NO, NO₂, carbon monoxide, carbondioxide, and combinations thereof; and e. purging the reactor with apurge gas, wherein steps b through e are repeated until a desiredthickness of the film is obtained.
 3. The method of claim 1 wherein R⁸is selected from the group consisting of nPr, iPr, nBu, iBu, sBu, tBu,isomers of pentyl, vinyl, phenyl, and alkyl substituted phenyl.
 4. Themethod of claim 1 wherein R⁹ is selected from the group consisting ofhydrogen, Me, Et, nPr, iPr, nBu, iBu, sBu, tBu, isomers of pentyl,vinyl, phenyl, and alkyl substituted phenyl.
 5. The method of claim 2wherein R⁸ is selected from the group consisting of nPr, iPr, nBu, iBu,sBu, tBu, isomers of pentyl, vinyl, phenyl, and alkyl substitutedphenyl.
 6. The method of claim 2 wherein R⁹ is selected from the groupconsisting of hydrogen, Me, Et, nPr, iPr, nBu, iBu, sBu, tBu, isomers ofpentyl, vinyl, phenyl, and alkyl substituted phenyl.